Apparatus for treating hydrocarbons to obtain high grade lubricating oils and lighter hydrocarbons



Dec. 24, 1935. w. L. GOMORY 2,025,384

APPARATUS FOR TREATING HYDROCARBONS TO OBTAIN HIGH GRADE LUBRICATING OILS AND LIGHTER HYDROCARBONS Filed Sept. 19, 1930 I 2 Sheets-Sheet 1 R O T N E V m Dec. 24, 1935. w. GOMORY 2,025,384

, !;-PPARATUS FOR TREATING HYDROCARBONS TO OBTAIN HIGH GRADE LUBRICATING OILS AND LIGHTER HYDRQCAHBONS' Filed Sept. 19, 1930 2 Sheets-Sheet 2 Q: m E a a "A 3 35 a l g s E k 5 k E l E E g a L E 51 Q N .{i a K g r k m S x 5 E as Q E I INVEN TOR.

agan-15a; 24, 1935 APPARATUS :FoR' TREATING HYDROCAR- BONS To OBTAIN men GRADE LUBRI- CATING OILS. AN

CARBONS D LIGHTER HYDRO- William L. Gomory, Paris, France, assignor to Standard Oil Development ration of Delaware Company, a corpo- Application September 19, 1930, Serial No. 482,919

1 Claim. ((31.196-78) This invention relates to the treatment of hydrocarbons to obtain high grade lubricating oils and lighter hydrocarbons and provides a process and apparatus whereby hydrocarbon oils of the most varied composition can be successfully treated in a continuous operation.

According to my invention the hydrocarbons are subjected in a heating and converting zone to the action of an excess amount of hydrogen or hydrogen containing gas or gas capable of liberating hydrogen or in the presence of substances capable of liberating hydrogen or hydrogen con-' taining gas or gaseous hydrocarbons and in the presence or absence of catalysts. Y

All of these alternatives, either singly or in any desired combination will be hereinafter referred to as hydrogen.

The heating andconverting zone may consist of a heating coil in connection with one or more conversion chambers or it may consist of a coil which forms a combined heating and converting zone, as described in my co-pending applications Serial Nos. 475,099 and 475,100, filed August 13, 1930 now Patents Nos. 1,933,108 and 1,934,056 respectively.

In hydrogenating hydrocarbons for the production of'lubricating oils great care has to be taken that the temperatures used are not too- The hydrogenated oil is extremely sensitive to heat treatment, thereiore it is very important to exactly regulate the temperature.

According to my invention, temperatures within the range of 500 degrees F. and 800- degrees F., but preferably Within the range of 550 degrees F. and 700 degrees F. are used depending upon the nature of .the oil to be treated and the oil is maintained in the conversion zone for the necessary length of time under regulated temperature conditions. 1 5

Should the temperature unduly rise in the conversion zone on-acccunt of the exothermic character of the reaction, the temperature of the contents of the conversion zone can be controlled by introducing regulated quantities of charging oil or intermediate hydrogenated products frominto the last section of'theheating coils at any i convenient point.

' The regulation of the temperature in the conversion zone can also be accomplished by passing the cooling medium through cooling coils located in the-conversion or hydrogenating zone,

The products under conversion are kept in vehement motion in the conversion zone by agitators or preferably by withdrawing the material from the conversion chamber and circulating it back to the conversion chamber.

The hydrogenated products from the heating and converting zone are discharged into a vaporizing zone in which a low absolute pressure is maintained.

Due to the relatively low temperature used in hydrogenating and the low absolute pressures maintained while distilling the hydrogenated products, very valuable lubricating oils are obtained.

The vapors obtained in the vaporizing zone are subjected to fractional condensation at a low absolute pressure and the various fractions are separately recovered and removed through cool.- ing coils into receivers in which a low absolute pressure is maintained;

The uncondensed gases together with the excess hydrogen are passed through an absorber in which the recoverable light products are absorbed with absorbent liquids such as, for instance, a gas oil of narrow boiling point range.

The gases which have not been absorbed in the absorber are conducted through a purifier to remove impurities such as, for instance, hydrogen sulfide and purified hydrogen is returned to the hydrogenating system.

The unvaporized residual oil is withdrawn from the vaporizing zone through cooling'coils into receivers in which a low absolute pressure is maintained.

' According to a modification of my process the heaviest condensate is withdrawn from the bottom of the first fractional condenser or dephleg mator irito an accumulator tank from which it is introduced, preferably through reheating tubes, into a vaporizing zone which is maintained under a preferably lower absolute pressure than that prevailing in the first mentioned vaporizing system.

- The unvaporized residual oil withdrawn from the first mentioned vaporizing zone is collected in an accumulator from which it is introduced, preferably throughreheating tubes, into a vaporizing zone in which a low absolute pressure is maintained preferably below that which prevails in the second mentioned vaporizing system.

In subjecting the heavier condensates with- I drawn from the fractional condenser or dephlegmator of the first mentioned vaporizing system to vaporization, the unvaporized residual oil is pref erably circulated from the vaporizing zone through the reheating tubes back into the vaporizingzone.

Furthermore, this unvaporized liquid can be conducted into the accumulator in which the unvaporized residual liquid oil from the first vaporizing zone is collected for further vaporization under lower absolute pressure conditions.

In subjecting the unvaporized residual oil to vaporization under very low absolute pressure conditions, this residual oil is preferably circulated from the vaporizing zone through the reheating tubes back into the vaporizing zone.

The vapors obtained from the second and third mentioned vaporizing zones are fractionally condensed and separately recovered as valuable lubricating oil fractions.

In cases where the hydrocarbons to be treated contain valuable light fractions, the hydrocarbons to be treated are first subjected to vaporization in order to remove the valuable light fractions contained therein and the residue obtained in this vaporization step is subjected to the action of hydrogen in the heating and converting zone.

The light vapors obtained in this vaporizing step are either introduced together with the hydrogenated productsinto the above mentioned first vaporizing zone or these vapors can be fractionally condensed in a separate fractional condenser and recovered separately after proper cooling.

In order that the invention may be fully understood reference will be made to the accompanying drawings which illustrate in diagrammatic form with parts in section, preferred apparatus for carrying out my improved process into practice.

Figure 1 illustrates diagrammatically one form of apparatus for carrying out my improved process.

Figure 2 shows a modification of the apparatus shown in Figure 1, wherein means are provided for separating excess hydrogen prior to subjecting the conversion products to vaporization.

The oil to be treated is drawn from any convenient source of supply I by means of a pump 2 and is forced through line 3 into preheating coil 4 located in the upper section of fractional condenser or dephlegmator 5, the oil then passing pipes and to insert and remove the catalytic ma- 7 terial.

Hydrogen is withdrawn from a suitable source of supply 99 by means of a pump I00 and is passed through line I0l, preferably through a heating coil l0l' which is heated in any suitable manner. The heated hydrogen is passed through mainline I02, through line I03 to the inlet end of the furnace coils I where it mixes with the oil passing through the coils.

Hydrogen can be also introduced from the main-line I02 into the furnace coils I at various intermedia e points and into the outlet thereof through lines I04 and I05.

The mixture of heated oil and hydrogen from aoaaesr.

the furnace coils l passes through line H and thence through line i2 into the thermally insulated conversion chamber Hi from which the products are withdrawn through lines 14 and i5 and pressure-reducing valve it and thence pass into vaporizer H.

In the drawings only one conversion chamber is shown but any number of conversion chambers can be used either in series or in parallel.

Hydrogen is introduced into the conversion chamber Hi from the main-line Hi2 through line to be used'are lower to enable to produce high grade lubricating oils.

The oil to be treated is heated in furnace coils l to temperatures within the range of 500 degrees F. and 800 degrees F., but preferably within the range of 550 degrees F. and 700 degrees F., de-

pending upon the nature of the oil to be treated 3 and the oil is maintained in the conversion cham her for the necessary length of time under regulated temperature conditions.

Should the temperature unduly rise in the conversion zone on account of the exothermic character of the reaction, the temperature of the contents of the conversion zone can be controlled by introducing from charging line 6 through line 6 regulable quantities of charging oil into conversion chamber I3 or into coil section II].

Intermediate hydrogenated condensates or hydrogenated residual oil can be also used for the regulation of the temperature in the conversion chamber or in the last section of the coils forming the conversion zone.

Such condensates can be introduced by pump i ll! through line I I0 into coil section l0 and through line H0" into line ll leading into conversion chamber I3.

Residual oil can be introduced by pump 5:

through line 53' into coil section II! and through line 53" into line H leading into conversion chamber 13.

The regulation of the temperature in the conversion chamber can also be accomplished by 7 passing charging oil through cooling cells 88 located in the conversion chamber I3, through line 6".

The products under conversion are kept in vehement motion in the conversion chamber by agitators or preferably by withdrawing the material from the conversion chamber and circulating it back to the conversion chamber with the aid of pump 81 through lines 86 and 86'.

The pressures employed usually will exceed atmospheric pressure. Pressures of pounds or more may be employed and higher pressures, such as for example 500 pounds to 3000 pounds or more may be used in carrying out the hydrogenating treatment.

The hydrogenated products entering the vaporizer, which is heavily insulated against heat losses, will vaporize in a greater or lesser extent depending upon the degree of absolute pressure denser or dephlegmator. and thence through line 20 into condenser 5'.

Fractional condensers 5 and 5' sulation and are provided with cooling coils'4 and 4 located in the top part of the dephlegmators, through which cooling medium (feed oil, water, etc.) can be passed to produce the necessary amount of condensation.

The fractional condensers or dephlegmators 5 and 5' are also provided in the bottom part with steam 'coils 2| through which live steam may be introduced, if desired, to assist in removing lower boiling fractions from the condensate accumulating in the botom of the fractional condensers.

In the drawings two fractional condensers are shown but a greater number of such fractionators can be used.

The vapors pass from the fractional condensers through line 22 into barometric condenser 23 .which is connected throughv line 22' with vacuum pump l8.

The gases discharged by vacuum pump I8 are passed with the booster pump 24 through line 25 to absorber 26 and from there through line 21 to 1 purifier 28 and the excess hydrogen gas, after 3| to the hydrogen supply 99.

Any lighter product which may have been condensed by water spray I01 in barometric condenser 23 is removed therefrom through line 32 intoseparator 33 from which it can be recovered.

Absorbing liquid, for example gasoil, is introduced through line 34 into absorber 26 and the absorbed products are removed through line 35.

Purifying liquid such as, for instance, alkaline solution is introduced through line 36 into purifier 28 and the liquid containing impurities is removed from the purifier through line 31.

Vaporizer I1 is also. provided with steam coil coil l'l" through which a cooling medium, for' instance feed oil, is passed to provide the desired regulation.

The residual oil obtained in vaporizer H is withdrawn through line 38 and line 39 and is passed through a cooler into a receiver which is connected to a vacuum pump (notshown) in exactly the same manner as the heavy condensate obtained in fractional condenser 5 is withdrawn through lines 4|] and 4| through cooling coil 42 and line 43 to receivers 44. These receivers are connected throughline 45 to vacuum pump 46 and can be used alternately in such a. manner that one of the tanks is used to collect the condensate while the condensate is withdrawn from the other tank through line 41.

Similarly the condensate collected in fractional condenser 5 is Withdrawn through line 48, cooling coil 49 and line 50 into receivers 5| which are are protectedv against outside variation of temperature by indesirable to recover 5 and withdrawn through line 40 may be returned through line 40' into vaporizer The vaporizer and fractional condensers are maintained under an absolute pressure, for ex-- ample between 15 to 50 m/m. mercury and in 5 some cases an absolute pressure preferably less than 15 m/m. mercury is maintained.

According to a modification of my invention the residue withdrawn through line 38 form vaporizer I1 is passed by pump 53 through line 54 to accumulator tank 55.

Accumulator tank 55 is provided with a'vente line 55' to allow the return to vaporizer ll of any vapors which might be evolved in accumulator tank 55.

The residual oil collected in accumulator tank 55 is passed through line 56 by pump 51 through line 58 and preferably through reheating tubes 59 to vaporizer 69. v

When the heat contained in the residual oil withdrawn from accumulator 55 is not sufiicient and the oil is passed through reheating tubes 59, the oil is heated therein to a temperature which is close to and preferably somewhat below the mean boiling point of the fractions contained in the residual oil.

The oil entering vaporizer 60 will vaporize at a greater or lesser extent depending upon the absolute pressure which ismaintained in vaporizer 6|) and the fractional dephlegmators 6| and 6 This absolute pressure is preferably lower than that maintained in vaporizer l1 and fractionators 5 and '5'.

Vaporizer 60 is properly insulated to avoid heat losses. Vaporizer 69 is provided with steam coil 60 through which live steam may be introduced into the vaporizer 60, if desired.

Sometimes it might be desirable to recover from vaporizer 60 a residual oil with certain specific composition and in order to enable to regulate the temperature of vaporizer 60, the same.

is provided in the top part thereof with a cooling coil 60" through which a cooling medium, for instance feed oil, is passed to provide the desired regulation.

The residual oil collected in vaporizer 60 can be withdrawn through lines 62 and 63 through cooling coils |5| into receivers |52 (only one receiver shown) which are connected with a vacuum pump fl53, in exactly the same manner as described above. 7

All the residual oil collected in vaporizer 69 can be recirculated through line 62, pump 64, line 65, through reheating tubes 59 into vaporizer 60.

The vapors obtained in vaporizer are led through line 66 into fractional dephlegmator 6| in which valuable lubricating oil fractions are obtained. v

The vapors from fractional dephlegmator 6| 60 pass through line 6'! into fractional dephlegmator 6| in which further lubricating oil fractions are obtained.

Fractional dephlegmators 5! and 5| are insulated against the influence of outside temperature variations andare provided with cooling coils 84 through which cooling medium (feed oil, or other oil, or water, etc.) is passed to cause the necessary degree of cooling and they are also provided with steam coils 85 through 70 which live steam may .be injected, if desired.

In the drawings two fractional condensers are shown but a greater number of such fractionators can be used. 4

The vapors leave fractional dephlegmator-6|.

and pass through line 69 into barometric condenser 69 which is connected to vacuum pump 18 through line 19'. The function of barometric condenser 69 is identical with that described in connection with barometric condenser 23.

The lubricating oil fraction obtained in frac= tional dephlegmator 6! is withdrawn through line 1|, cooling coil 12, line 13 into receivers M which are connected through line 15 to vacuum pump 16.

The lubricating oil fraction obtained in fractional dephlegmator Si is removed through line 11, cooling coil 18 and line 19 into receivers 89 which are connected through line 8i to vacuum pump 16.

Receivers 14 and til are used in such a mannor that one of the receivers 14' and 86 respectively is used to collect lubricating oil fractions while the liquid is removed from the other receivers through lines 82 and 83 respectively.

According to a further modification of my process, the condensate obtained in fractional condenser 5 and removed through line 49 is passed by pump H into accumulator III. Accumulator III is provided with vent-line II I to allow the return to vaporizer I1 of any vapors which may be evolved in accumulator I I I.

The condensate is conducted from accumulato-r III through line H2 by the aid of pump H3, through line I I4 and preferably through reheating tubes H5 into vaporizer H6.

When the heat contained in the condensate withdrawn from accumulator I I I is not suflicient and the oil is passed through reheating tubes H5, the oil is heated therein to a temperature which is close to and preferably somewhat below the mean boiling point of the fractions contained in the residual oil.

The oil entering vaporizer H6 will vaporize at a greater or lesser extent depending upon the absolute pressure which is maintained in vaporizer H6 and the fractional dephlegmators H1 and H1.

This absolute pressure is preferably lower than that maintained in vaporizer I1 and fractional dephlegmators 5 and 5', but preferably somewhat higher than that prevailing in vaporizer 60 and fractional dephlegmators BI and 6|.

Vaporizer H6 is properly insulated to avoid heat losses and is provided with steam coil H6 through which live steam may be injected in vaporizer H6, if desired.

Sometimes it might be desirable to recover frori vaporizer H6 a residual oil with certain specific composition and in order to enable to regulate the temperature of vaporizer H6, the same is provided in the top part thereof with a cooling coil H6 through which a cooling medium, for instance feed oil, is passed to provide the desired regulation.

The residual oil collected in vaporizer H6 can be withdrawn through lines H8 and H9 through cooling coils I54 into receivers I55 (only one receiver is shown) which are connected to vacuum pump I56 in exactly the same manner'as described above.

Or the residual oil collected in vaporizer H6 can be recirculatedthrough line H8 and pump I20, line I2I through reheating-tubes H5 into vaporizer H6.

The vapors obtained in vaporizer H6 are led through line I22 into fractional dephlegmator H1 in which valuable lubricating oil fractions are obtained.

The vapors from fractional dephlegmator H1 aoaasea pass through line I23 into fractional dephlegmator I I1 in which further lubricating oil fractions are obtained.

Fractional dephlegmators H1 and H1 are insulated against the influence of outside tempera- 5 ture variations and are provided in the top thereof with cooling coils I24 through which cooling medium,- for instance feed oil, is passed to cause the necessary degree of cooling and they are also provided in the bottom part thereof with steam coils I25 through which live steam may be injected, if desired.

In the drawings two fractional condensers are shown but a greater number of such fractionators can be used. I

The vapors leave fractional dephlegmator H1 and pass through line I26 into barometric condenser I21 which is connected to vacuum pump I28 through line I28.

The function of barometric condenser I21 is identical with that described above in connection with barometric condenser 23.

The lubricating oil fraction obtained in fractional dephlegmator H1 is removed through line I29, cooling coil I30, line I3I into receivers I32 which are connected through line I33 to vacuum pump I34.

The lubricating oil fraction obtained in fractional dephlegmator H1 is removed through line I35, cooling coil I36 and line I31 into rec ivers I38 which are connected through line I39 to vacuum pump I34.

Receivers I 32 and I 38 are used in exactly the same manner as described above in connection with receiver tanks 44, 5| and 14, 8D.

In cases where the hydrocarbons to be treated contain valuable light fractions, such hydrocarbons are treated according to a further modification of my. process in which the feed oil is passed by the aid of feed pump 2 from supply tank I 40 through line 3 and cooling coil 4 and line 6 through line 89 into still 90 in which it is spread on tray 9|.

Still 90 is provided with steam coil 92 through which live steam may be introduced into the oil contained in the still, and still 90 may be also directly heated. Obviously instead of still 96 shown in the drawings, any other method (for instance a vaporizing system consisting ,of a heating coil connected with a vapor tower) can be used in order to separate the light fractions contained in the oil to be treated.

The light fractions obtained in still 90 are removed through line 93 and are conducted through lines 94 and I5 to pass through pressure-reducing valve I6 into vaporizer I1 in such a manner that these vapors are mixed with the hydrogenated products passing from the hydrogenating system into the vaporizing system.

The vapors obtained in still can also be separately removed therefrom through lines 93 and 95 and led to a condensing and cooling system (not shown) from which the condensate can be separately removed.

The unvaporized residue from still 90 is passed through line 96 and is conducted by the aid of pump 91 through line 98 into furnace coils 1 to be treated exactly in the same manner as described above. I

Figure 2 shows another modification of my process according to which the products obtained in the hydrogenating step can be freed from all or greater part of the excess hydrogen and 75 aoeaese the low boiling point products before subjecting the hydrogenated products to subatmospheric distillation.

In this case the hydrogenated products are discharged through line E i'from the hydrogenating system through line iili into separator iii in which the temperature and the pressure are so regulated that only the most volatile hydrocarbons will be vaporized and removed from the separator together with the excess hydrogen.

The temperature in the separator can be regulated in any known manner, for instance by passing cooling medium through coils! E2.

The vapors together with the excess hydrogen are passed from separator iil' through line i F3 and line 25 through absorber 26 in which the recoverable light products are absorbed and the gases which have not been absorbed are conducted through line 27 through purifier 28 and the purified hydrogen is returned to the hydrogenating system through line 29, booster pump 3% and line 3i.

The hydrogenated products freed from the ex= cess hydrogen and the low boiling point products are conducted through line I'M, by pump I'M preferably through reheating tubes H and. through line 15 into vaporizer H which is maintained under sub-atmospheric pressure.

When the heat remaining in the hydrogenated products is not sufiicient and they are passed through reheating tubes I15, they are heated therein to a temperature which is close to and preferably somewhat below the mean boiling point of the fractions contained in the hydrogenated products. The direct passage of hot hydrogenated products to a vaporizer and the subsequent treatment of the fractions vaporized therein is claimed broadly in my co-pending application, Serial No. 475,099. filed August 13, 1930 and allowed April 19, 1933. The present application is directed specifically to the operation of the vaporizer at sub-atmospheric pressures and to the subsequent distillation of the vaporizer residue.

I have described and shown preferred form of 5 the apparatus and various modifications of the use of my invention but it is to be understood that there are possible modifications without departing from the spirit of the invention and I wish to claim as broadly as it is permitted by the prior art, the invention covered in the appended claim.

I claim:

Apparatus for the production of high grade lubricating oils, which comprises heating means I and means for supplying oil under pressure to the inlet of said heating means, means for supplying heated gas rich in free hydrogen to the inlet and outlet of said heating means and to various intermediate points thereof, a fourth means adapted to maintain the oil and gas under subatmospheric pressure and at a high temperature and provided with a circulating pump connected to the bottom and top part thereof, vaporizing means into which the hot oil from said fourth means is directly discharged, said vaporizing means being adapted to be maintained at subatmospheric pressure and being provided with outlets for vapors and liquids, the vapor outlet from said vaporizing means being connected to a fractional condenser provided with liquid and va- 30 por outlet connections, the vapor outlet connection from the fractional condenser being connected to a barometric condenser which is connected with a vacuum pump, the liquid outlet of said vaporizing means being connected by a. pump to a reheating and vaporizing system, said vaporizing system being provided with means to maintain sub-atmospheric pressures therein.

WILLIAM L. GOMORY. 

